Anthraquinone carbonyl hydrazines



Patented Sept. 4, 1951 s PATENT "OFFICE ANTHRAQUINONE CARBONYL HYDRAZINES; r

" Frederic B. Stilmar, Wilmington, Del., assignor-to E. Ldu Pont" de Nemours & company, Wilmington,,.Del., a corporation of Delaware Draw This invention relates to the preparation of a new class of compounds of the anthraquinone series, and more particularly new acylated l-aminoand 1-nitroanthraquin0ne-2carbonyl hydrazines. r a

. The anthraquinone vat dyes are known to be of particular value because of their excellent fastness properties, and, while a large-range of colors has been produced commercially, there has not been produced a red dye in this class which will dye in the'bright shades'desirable' and have the good fastness' properties of dyes ofthis class ingeneral. Se'veral red dyes have been produced in the anthraquinone series, but they lack thef'strength or brightness or certain fastness Application MarchvlS;1949, SerialNo.81,618 1,;

4.0mm. wretogs'si j;

properties which are particularly desirable and which usually "identify the dyes of this class."

It is an object of the present invention to produce axclass of new compounds which, although exhibiting dye properties in themselves, are partion of bright red dyes of the anthraquinone vat dye class which exhibit excellent fastness prop erties' and high tinctorial'strength, A more spe- Tcific object of the invention is to produce acylated l-aminoand 1-nitroanthraquinone-2-carbonyl hydrazines from organic dicarboxylic acid chlorides of the formula:

in which R stands for a radical of the group consisting of benzene, naphthalene, diphenyl and terphenyl radicals and the benzene, naphthalene, diphenyl and terphenyl groups containing from 1 to 4 halogen atoms of the group consisting of chlorine and bromine.

The compounds of this invention are prepared by v reacting 1aminoanthraquinone-2-carbonyl hydrazine or l-nitroanthraquinone=2-carbonyl hydrazine with an acid chloride of an aromatic dicarboxylic acid of benzene, naphthalene, diphenyl or the terphenyl series, any of which may contain up to 4 halogen atoms. The reaction is preferably carried out at elevated temperatures in an inert solvent such as nitrobenzene or the chlorobenzenes, giving high yields of acylated hydrazines of the general formula:

tit 15% ticularly usefulas intermediates in the preparain which Yfstan ci s for a substituent of the group consisting ot -Nliz and iNO2 and R has the same significance as given in, theprecedingformula. i

The acylated anthraquinone hydrazines of this invention are particularly valuable in the manufacture of bis-anthraquinone-oxdiazoles which are bright red-to-scarlet vat dyes. This latter class of dyes is produced by subjecting the bisacylated hydrazides tothe action of acid condensing agents such as thionyl chloride, phosphorus oxychloride, p-tolu'ene sulfonic acid, etc., whereby-ring closure of the hydrazide groups to oxdiazole rings effected. These dyes are more particularly disclosedand claimed in co-pending application Serial No. 81,619, filedMarch 1 5, 1949,'now =U. S.:Patent 2,511,018,

The following examples are given to illustrate I the invention.- The parts used are by weight, un-

benzene and dried. It has a melting point of from 299 to 304 C., and may be represented by the E formula:

. It dyes cotton from an. alkaline hydrosulfite vat inweak red shades that. change to blue-violet on treatment with alkali.

Example 2 Five (5) parts of isophthalic acid is converted to the acid chloride by heating with 250 parts of trichlorobejnz'ene.and 10 parts of thionyl chloride under reflux at C. until solution is complete; then the excess thionyl chloride is removed by air blowing; To the resulting solution 20.5 parts of 1-nitroanthraquinone-2-carbonyl hydrazine are added and the temperature maintained at -170 C. 'for four hours.

The resulting colorless product dyes cotton from an alkaline hydrosulfite vat in weak red shades. It has the formula:

Example 3 Five and four-tenths (5.4) parts of naphthalene-lA-dicarboxylic acid is converted to' the acid chloride by heating with 10 parts of thionyl chloride and 200 parts of nitrobenzene. air-1'50 155 C. for four hours. The excess thionyl chloride is removed by air blowing, and 17 parts of l-nitroanthraquinone-2ecarbony1 hydrazine are added. After heating at 160-165 C. for several hours, the resulting" almost colorless particles are filtered off, washed with benzene and'dried. This product has the formula:

h) NO Example 4 Five (5) parts of diphenyl-A' dicarboxylic acid is converted to the acid chloride by heating with parts of thionyl chloride'and 200'parts of nitrobenzene at 145 C'.-forten hours. Bythat time solution is complete, and the excess thionyl chloride is removed by air blowing.

Twelve and three-tenths (12.39 parts of l-nitroheated to 1'60'I70 C. for two hours.

4 zine is complete. The product, which is obtained in high yields, has the formula:

Example 6 Qne ('1) part of terephthalyl chloride, 5.6 parts of. l aminoanthraquinone 2 carbonyl hydrazine and 100 parts of nitrobenzene are The red crystalline product is filtered off, washed with benzene and dried. It is obtained in good yields and has the formula:

anthraquinone-2-carbonyl hydrazine are added to the solution, and after heating at 160-1'70 C. for several hours the resulting product, as microscopic needles, is isolated by filtration, washed with benzene and dried. It-has a melting point p of 308 C. and the formula:

In place of diphenyl-4,4-dicarboxylic acid, p-terphenyl-4,4"-dicarboxylic acid may be used to give the corresponding p-terphenyl compound having similar reactivity and chemicalproperties.

Example 5 Ten (10) parts of chloroterephthalic acid is convertedinto the d'icarbonyl chloride by refluxingwith 25 parts of thionyl chloride, 400 parts. of o di'chlorobenzene and part: of pyridine at BOP-140 C. for three hours- The excess thionyl chloride is removed by a current of. air, andthere isadded 34.1 parts of l-nitroanthraquinone-Z- carbonyl hydrazine.

After heating at 160-1 70 C. for two. hours,

the formation of the white bis-acylated hydradried. The tetrach'loro compound is;- obtained in good yields and has. the" formula:

N01. 01 G1. V N'H-N I If H In place of the particular dicarboxylic acid chlorides used in the above examples, there may be substituted other chlorine or bromine substituted dicarboxylic acids of the benzene, naphthalene, diphenyl or terphenyl series. to give products which likewise have dye properties in themaura selves but which are more particularly valuable for intermediates in the preparation of o'xdiazole dyes as more particularly described above. As further illustrative of the dicarboxylic acid chlorides which may be employed, may be mentioned:

It will be obvious that only those dicarboxylic acids or acid chlorides can be employed which do not form cyclic imides with hydrazines. In other words, the terephthalyl chloride, the isophthalyl chloride and their chloro or bromo derivatives, the 1.3-, 1,4-, 1,5-, 1,6- or 1,7-naphthalene dicarboxylic acids, and any of the diphenyl and terphenyl dicarboxylic acids which have the carboxylic acid groups separated by at least three carbon atoms if they are both on the same benzene ring], or separated by at least 5 carbon atoms if they are on different benzene rings in the molecule, may be employed. In other words, the obenzene ."dicarboxylic acid, the naphthalene-1,8- dicarboxylic acid and the 2,2-diphenyl or the 2,2-terphenyl dicarboxylic acid which form cyclic imides with hydrazines, are not satisfactory for producing the compounds of the present invention.

The compounds of this invention may be ring closed without isolation from the nitrobenzene or other solvent mass by adding the acid condensing agent such as thionyl chloride, and continuing the heating at temperatures of from 160- 170 C. to produce the oxdiazoles as more particularly disclosed in my eo-pending application Serial No. 81,619 filed March 15, 1949, now U. S. Patent 2,511,018.

As illustrated in the above examples, the dicarboxylic acid chloride may be formed as a preliminary step in the preparation of the condensation product without isolation from the organic solvent in which it is formed, although where preferred it maybe first prepared in any desired manner and, after isolation, condensed with the anthraquinone-il -carbonyl hydrazine. It will be obvious that other acid halides can be employed in place of the acid chloride.

By vatting the nitro compounds produced from the 1-nitroanthraquinone-2-carbonyl hydrazine with sodium hydrosulfite and caustic,

they may be converted to the corresponding amino compounds. Usually, however, it will be found desirable to effect ring closure of the nitro compounds prior to their reduction to the amines.-

I claim:

1. The anthraquinone carbonyl hydrazines of the general formula:

t t t il l I I in which R stands for a radical of the group consisting of 1,4-phenylene, 1,4-naphthylene and 4,4-diphenylene radicals and their halogen derivatives which contain from 1 to 4 halogen atoms of the group consisting of chlorine and bromine, and in which Y stands for a substituent of the group consisting of -NH2 and -NO2.

2. The anthraquinone carbonyl hydrazine of the formula:

N02 1|-IO2 O ii ii 3. The anthraquinone carbonyl hydrazine of the formula:

4. The anthraquinone carbonyl hydrazine of FREDERIC B. STILMAR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Stihnar Mar. 22, 1949 Number 

1. THE ANTHRAQUINONE CARBONYL HYDRAZINES OF THE GENERAL FORMULA: 